Carboxylic acid-polyethylene polyamine reaction mixture



: Patented June 11, 1963 United States Patent "See 3,093,655

r t and the temperature rises to about 100 C. due to salt 3,093,655 formation. CARBOXYL ACID-POLYETHYLENE POLY Immediately after adding all of the triethylene tetra- Elizabeth c near ii -ii o s t if and lhilip K Isaacs mine System is Protected during y e i against Brookfine;Mass assinors to R Grace & Ci), 5 catalyhcpro-oxidant metals by the addition of a chelatbridge, Mass., a corporation of C ti t i g and inactivating agent. These metals, which are in- No Drawing. Filed Dec. 28, 1960, Ser. No. 78,873 U llc d as impurities in the acid and amine reactants, 3 Claims. (Cl. 260--309.6) catalyze degration of the reaction product with a resulting increase in viscosity and darkening of the product. Even This invention relates to compositions containing a small leaks in the packing surrounding the agitator shaft complex compound having a plurality of imidazoline through which atmospheric oxygen can gain entrance into rings as a principal constituent. In another aspect it the mixing vessel can cause a tenfold increase in the visrelates to a method fortpreparing such compositions by cosity. The agent is added in amounts suflicient to react contacting a plurality of diverse carboxylic acids and a with substantially all of the metallic impurities present polyethylene polyamine under reactive conditions. in the reactants and generally between 0.1 percent to Monoimidazolines, such as u ndecylimidazoline, and di- 0:5 percent by weight based on the total weight of the imidazolines, such as octamethy-lene diimidazoline, are acids and amines has been found satisfactory. Suitable known but have limited utility. The complex polyimidagents include the alkali metal polyphosphates, such as azoline of this invention contains a terminal primary sodium and potassium tripolyphosphate.

amino group (-NH has a high molecular weight, is 0 The mixture is then heated at 1 atmosphere to about The present compositions are prepared by heating oleic and sebacic acids and triethylene tetramine at reduced giih iril giig Temperature, Pressure, pressures under nitrogen while v1gorously agitating the reeaction mixt rg 0, mm. Hg actants. Imidazoline formation proceeds essentially in fi t i two steps. In the first step, a terminal amino group of the polyamine reacts with a carboxyl group to form an 20 152 5 t 585 amide with the release of one mole of water. Then, a t 152.5 435 second mole of water splits out from the amide group 23 and a secondary amino group beta to it, causing cycliza- 100 132.5 135 tion to give an imidazoline. Dicarboxylic acids reacting K3 $33 5 &2 with polyamines in this manner-produce a complex poly- I 160 -5 1 r 35 imidazoline containing imidazoline rings plus some amide r 180 15 strongly basic, and possesses strong surface activity.v 150 C. at which point the pressure and temperature are When incorporated with a polymeric material, such as adjusted periodically in inverse relationship according polymers and copolymers of vinyl chloride, it performs to the following schedule:

admirably as a curing agent.

groups and secondary amino groups resulting from incomplete cyclization. The overall reaction yields a mix- Since water catalyzes side reactions and hydrolyzes imidture comprising a major amount of (1) a polyimidazoline 4 azolines, it is removed as it is formed in order to achieve having the following idealized structure: maximum conversion to imidazoline. The above sched- H O1 H -h3--N-GHg-OH:N0-0sH s?NOH:OH:l I-CH OH -NH,

N H1 H1 N\ H:

\OH: O I O l in which up to about 15 percent of the original carboxy-l ule permits removal of water as fast as possible consistent groups are 1n the form of unconverted amldes with imidazoline conversion without distilling appreciable H I amounts of tetramine. During the reaction period, the agitator should be run at a high rate of speed to give a H H o C high surface turnover of the mixture for rapid water redenved from th TeactlOIl of acid Wlth Prlmary amine mov-al. An agitator speed of about 100-200 r.p.m. has

groups: and/01' Nsubstimted amides been found to be satisfactory. Experiments have shown that low water removal caused by decreasing the speed 5 from about 150 to 65 r.p.m. lowered the imidazoline content by about lO percent due to irreversible hydrolysis of the imidazoline ring.

After a temperature of about 220 C. and a pressure derived from either hydrolysis of previously formed imidazoline rings or the reaction of acid with secondary amine groups, and/or '(2) species of imidazolines and P about 15 Hg have 3 Teached wlthm three polyimidazolines having higher and lower molecular hours according to the foregoing schedule, this pressure weights than the molecule. weight of the idealized p01} and temperature are held and the reaction mixture is imidazoline structmm heated further for about one hour under these condi- In carrying out the invention, the ol i id i fi t tions. Thereafter the product is cooled to 150 C. under charged a glassilined mixing vessel and then the nitrogen and collected. The viscos ty of the reaction sebacic acid is stirred in. Agitation is continued through- Product average? about 1,000 centlPolses at The out the reaction period. The acid mixture is deoxygenaverage COmPOSItiOII as determined y infiraled pd at a pressure f about 15 H h vacuum i tion analysis is comprised of structures resulting from 85 released with nitrogen and a blankcting stream of nitro- Wment Conversion of thfi carboxyl gTOIIPS t0 imidaZOlille gen is thereafter used throughout the reaction. Follow- 7 rings with the remaining 15 percent of the carboxyl ing deoxygenation, the acids are heated to about C., 0 groups existing as amide groups. the requisite amount of triethylene tetramine is added The molar quantities of acids and amine used to prepare the reaction mixtures are 1 mole of oleic acid, 1

mole of sebacic acid and 2 moles of triethylene tetrarnine.

The invention is furtherillustrated by the following examples:

Example 1 82.6 lbs. (0.2925 mole) of oleic acid were charged to a glass a vacuum vessel and then 59. 1 lbs. (0.2925 mole) of sebacic acid were added. The acids were heated to about 7 C. and then 85.5 lbs. (0.5850 mole) of triethylene tetramine were added. Due to the exothermic nature of the reaction between the amine and acids, the temperature of the mixture rose to about 100 C. 0.23 lb. of powdered sodium tripolyphosphate was then added as a metal chelating agent. Vigorous agitation and a nitrogen atmosphere were maintained throughout. The mixture was then heated at 1 atmosphere to about 150 C. and the temperature and pressure were carefully controlled thereafter for a'four-hour period according to the pressure-temperature schedule set forth hereinbefore. During this period, water of condensation was continuously removed to avoid hydrolysis of the imidazolines. The amount of water removed over the entire reaction period corresponded with about 85 percent conversion of the carboxyl groups to imidazoline groups, leaving a balance of about 15 percent of the carboxyl groups in the form of amides. The composition of the reaction mixture was confirmed by infrared absorption analysis. Finally, the product was cooled under nitrogen to about 130 C.

The utility of the reaction product is demonstrated in the following Example 2:

Example 2 1 part by weight of a product prepared according to Example 1 was admixed with 4 parts by weight of epoxidized soybean oil having an oxirane oxygen content of 7.0 percent. The mixture was heated for about 1 hour at about 130 C. and gave a reaction product which was fluid at room temperature. 63 parts of the fluid reaction product were then compounded with 50 parts of Geon l-mlnute 3-minute cure cure Approximate number of crosslinks per 10,000

molecular weight 1. 5 4. 0 Percent extraction by cyclohexanone l0 8 It is noted that the acids-amine reaction mixture of this invention gave a highly-crosslinked polymer which was cured in a very short period of time. The very low cyclohexanone extraction value renders the polymer suitable for use as a solvent resistant gasketing material.

We claim:

1. A composition derived by reacting in a deoxygenated system 1 mole of oleic acid, 1 mole of sebacic acid and 2 moles of triethylene tetramine at a temperature of about C. to 240 C. and a pressure of about 10 to 760 mm. Hg while continuously removing the water of reaction, and continuing the reaction until the flow of water of reaction substantially ceases.

2. A composition according to claim 1 wherein the reaction is carried out in the presence of a small amount of a chelating agent.

3. A composition according to claim 2 wherein the chelating agent is sodium tripolyphosphate.

References Cited in the file of this patent UNITED STATES PATENTS 2,374,354 Kaplan Apr. 24, 1945 2,568,876 White et al Sept. 25, 1951 2,668,165 Carpenter Feb. 2, 1954 2,846,440 Hughes Aug. 5, 1958 2,917,376 Stromberg et a1 Dec. 15, 1959 

1. A COMPOSITION DERIVED BY REACTING IN A DEOXYGENATED SYSTEM 1 MOLE OF OLEIC ACID, 1 MOLE OF SEBAIC ACID AND 2 MOLES OF TRIETHYLENE TETRAMINE AT A TEMPERATURE OF ABOUT 50*C. TO 240*C. AND A PRESSURE OF ABOUT 10 TO 760 MM. HG WHILE CONTINUOUSLY REMOVING THE WATER OF REACTION, AND CONTINUING THE REACTION UNTIL THE FLOW OF WATER OF REACTION SUBSTANTIALLY CEASES. 